Dialkylaminosulfur trifluorides as fluorinating agents

ABSTRACT

Dialkylaminosulfur trifluorides such as diethylaminosulfur trifluoride are useful in replacing hydroxyl group and carbonyl oxygen with fluorine in various organic compounds.

United States Patent Middleton Oct. 21, 1975 [54] DIALKYLAMINOSULFUR TRIFLUORIDES [56] References Cited AS FLUORINATING AGENTS UNITED STATES PATENTS Inventor: William J p Middleton, Chadds 3,705,897 12/1972 Murphy 260/243 c Ford, Pa. [73] Assigneez L Du Pom de Nemours & Primary Examiner-Nicholas S. Rizzo Company, Wilmington, Del. Attorney, Agent, or FirmAnth0ny P. Mentis [21] Appl. N0.: 314,022 Dialkylaminosulfur trifluorides such as diethylaminosulfur trifluoride are useful in replacing hy- [52] US Cl 260/397 3 260,482 C; 26O/469; I droxyl group and carbonyl oxygen with fluorine in var- 260/465.6; 260/544 B; 260/562 B; gamc 260/609 R; 260/644; 260/601 H; 260/633; 260/653; 260/73 L; 260/9l.3 R; 260/212; 260/239.1 [51] Int. Cl. C07D 501/20 4 Claims, No Drawings [58] Field of Search 260/243 C, 465.6, 397.3,

260/469, 633, 609 R, 653, 562 B, 601 H, 482 C, 644, 544 B DIALKYLAMINOSULFUR. TRIFLUORIDES AS FLUORINATING AGENTS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a new process for preparing organic fluorine-containing compounds. More particunating agents. The use of sulfur tetrafluoride is disclosed in U.S. Pat. No. 2,859,245 and US. Pat. No. 2,983,626. W. C. Smith, Angew. Chem. 74, 742 (1962) presents a review of its use. W. A. Sheppard, J.A.C.S. 82, 4751 (1960); 84, 3059 (1962) describes the use of phenylsulfur trifluoride. Fluoroamine reagent, (CI-I -NCF CFI-ICl, has also been used. All of these reagents are not completely satisfactory for one reason or another.

The dialkylaminosulfur trifluorides have been previously reported in the literature but no mention has been made of their use as fluorinating agents. The following are mentioned:

1. G. C. Demitras, R. A. Kent and A. C. MacDiarmid, Chem. Incl. (London), 1964, 1712; and G. C. Demitras and A. G. MacDiarmid, Inorg. Chem., 6, 1903 (1967). These papers describe the preparation of (CH NSF by the reaction. of SF, with (CH ),NSi(Cl-l The "F nmr spectrum was described.

2. S. P. Von Halasz and O. Glemser, Chem. Ber., 103, 594, (1970), show the preparation of (C HQ NSF by reaction of (C l-l NSi(CI-I with SF.,. This compound reacts with (Cl-I ),,Si-N=C=N-Si(CH to give NCN=SFN(C H No other chemistry is reported.

3. S. P. Von I-Ialasz and O. Glemser, Chem. Ber., 104, 1247 (1971), describe the preparation of RSI} (R Me N, Et N and piperidino) by the reaction of R- Si(CH with SP No fluorination reactions are disclosed.

DESCRIPTION OF THE INVENTION It has now been found that a compound of the Formula wherein each of R and R, alike or different, is a primaryalkyl group of up to 4 carbon atoms, or when taken together are (Cl-I or -(CH will react with an organic compound containing hydroxyl and/or carbonyl groups to replace such groups with fluorine. The reaction can be carried out under mild conditions that are often not suitable with known fluorinating agents. For example, the reaction can be run in glass equipment at atmospheric pressure and without the use of an acid catalyst as may be required with SP In general, organic compounds that contain hydroxyl and carbonyl functions will react with dialkylaminosulfur trifluorides to give organic fluorine compounds. These compounds include monomeric alcohols, aldehydes, ketones, and carboxylic acids containing up to 40 carbon atoms and which may be monofunctional or polyfunctional. Organic polymeric compositions that contain hydroxyl or carbonyl groups, such as cellulose and vinyl alcohol homopolymers and copolymers, can also be fluorinated with dialkylaminosulfur trifluoride.

The hydroxyl compounds that can be used in this process include monofunctional and polyfunctional aliphatic primary, secondary, and tertiary alcohols and aromatic, heterocyclic, and aliphatic carboxylic acids, all of .which may contain other substituents.

The carbonyl compounds that can be used in this process include aliphatic, heterocyclic, and aromatic ketones, aldehydes, and carboxylic acids which may also contain other substituents.

Included also are compounds that contain both hydroxyl and carbonyl functions in the same molecule. In addition to compounds specifically illustrated below by example or structural formula, the following compounds can be used in the process of this invention.

Examples of alcohols that may be used are methanol, ethanol, cyclopentanol, phenylethyl alcohol, isopropanol, tert-butanol, stearyl alcohol, polyvinyl alcohol,

I glycerin and cholesterol.

Examples of aldehydes that may be used are formaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, phthaladehyde, piperonal, dodecyl aldehyde, n-butyraldehyde, isobutyraldehyde, glyoxal, anthraldehyde, anisaldehyde, acrolein, cinnamaldehyde and crotonaldehyde.

Examples of ketones that may be used are acetone, cyclohexane, 2-butanone, di-n-hexyl ketone, phorone, pinacolone, and acetonaphthone.

Examples of carboxylic acids that may be used are acetic, succinic, maleic, methacrylic, propionic, acrylic, stearic, glutaric, phenylacetic, and naphthoic acid.

Although esters, amides and phenols are operable in this reaction, they do not work as well as alcohols, aldehydes, ketones and acids.

Generalized equations for the process of this invention are given below, with Q, X and Y representing the radicals of any nature whatsoever attached to the carbon containing the oxygen function to be replaced.

with a dialkylaminosulfur trifluoride is conducted under substantially anhydrous conditions. The reaction vessel can be made of metal, glass, plastic or ceramic sions to exclude moisture arej ta kenl.

The reaction is conductedfby charging th'eL dialk-T I ylaminosulfurtrifluoride into the: reaction vessel and then adding the hydroxyl orfca'rbonyl compound. Alternatively the hydroxyl or carbonyl compound can becharged first, or the hydroxyl or carbonyl compound and the dialkylaminosulfur trifluoride can be. charged simultaneously. Solvent is not necessary for the reaction, but the use of a solvent is usually advantageous to moderate the reaction. Either'or both of the reactants may be dissolved in an inert solvent before mixing or the reactants may be charged into an inert solventcon tained in the reaction vessel.

Solvents suitable for the reaction include hydro ca rbons such as benzene, xylene, pentane, hexane, decalin and isooctane; halocarbons such asmethylhe' chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene, trichlorofluoromethane; lethers such as' diethyl ether, dioxane, tetrahydrofuran, ethyl ene glycol dimethyl ether, an d di ethylene glyc ol dimethyl ether; nitriles such as acetonitrile and bnzonitrile; nitro compounds such as nitro'm ethane and nitrobenzene; or any solvent inert to both of the reactants.

The reaction is conducted at temperatures from 100 to +100. The preferred range for replacing hydroxylgroups is from 80 to +35, and the preferred range for carbonyl compounds is from to -l-80. The time of reaction is generally dependent on the temperature and reactivity of the organic oxy or 0x0 group. Times of an hour or less to a week can be us'ed.

Pressure is not critical. Ambient and/or autogenous pressures are the most convenient and therefore preferred.

The mole ratio ofreactants' is normally chosen for maximum yield, 'with one equivalent of 'dialkylaminosulfur trifluoride needed for each equivalent of hydroxyl or carbonyl present. When more than onehydroxyl or carbonyl group is present in thecornpound to be fluorinated, the more reactive groups can be'se1ectively reacted by adding the dialkylaminosulfur trifl'uoride to an excess of the po lyfunctional compound, preferably in a solvent to 'insure good mixing. l

The fluorinated products can be separated from the reaction mixture and then purified by any of several standard methods, including distillation, chromatography, solvent extraction, and recrystallization.

The fluorine-containing compounds obtained by this process are gasses, liquids, or solids that have many uses. They can be used as gaseous or liquid carriers in aerosol sprays. They can be used as solvents and thinners in lacquers and paints. They are useful as liquid media for the preparation of dispersionsof carbon black and graphite and some are useful as insecticides. They can be used as heat transfer fluids and refrigerants. Most importantly, they can serve as intermediates in the preparation of other fluorine-containing compounds which are otherwise difficult to obtain, including pharmaceuticals, herbicides, insecticidesfand other pesticides. The polymeric fluorine-containing products prepared by this process are useful for construction of water and oil resistant objects, such as films and in preparing water and oil resistant coatings.

lngeneral, the dialkylaminosulfur;trifluorides,can be lane with sulfur tetra fluoride ata low temperature in an 65. prepared by the reaction of a,dialkylaminotrimethylsh v tion of diethy lamino and.dirnethylaminosulfur trifluoride. The preparation of these, as well as of piperidin'osulfur trifluoride, has also been reported by Halarz et mole) of sulfur tetrafluoride in 200 ml of trichlorofluoromethane at to 60. The reaction mixture was warmed to'room temperature and then distilled to give 88.86 g (84% yield) of diethylaminosulfur trifluoride as a pale yellow-fliquid, 15p 16 47? (10 mm)..;

' A ExAMEL'E- l 1. Dimeth ylaminos ul fui ,Trifluoride A solution of, 40 g mole) of dimethylaminotrimethylsilane in 50 ml CCI F was added dropwise ,to a solution of 20ml (measured at 78, 0.36 mole) of sulfurtetrafluoride in "1O0'1nlCCl F at -65? to -80. The reaction mixture wasdistilled'togive 37 g of dim 'e thylaminosulfur trifluoride as a pale yellow liquid,

4949.5 (33 mm); H nmr (CCl F) 8 3.07 pprn (s).

IISPECVIFICY EMBODIMENTS OF THE INVENTION 111' the illustrative-examples below, all parts are by weight unless otherwise stated.

EXAMPLE 1 1 Fluorooctahe A solution of 13.0 g (0.1 riiole) of l-octanol in 25 ml of methylene chloride was added dr opwise to a solution of 16.1 g (0.1 mole) of diethylaminosulfur trifluoride in 60 ml methylene chloride cooled to 7 0 to 65". The reaction mixture was then warmed to 25 and 50 ml of: water was added.- The.lower- ;orga'n'ic layer was separated, dried (-MgSO and then distilled to give Anal. calcd for "c.,n;,r. c, 7267,11," 12 .97; P, 14.37.

Found: c, 72.76; H, 13.09; F, 14.44.

EXAMPLE 2 Ethyl 2-Fluoropr'opionate A solution of 1.18 g (0.01 mole) of ethyl lactate in 2 ml of methylene chloride'= was'- slowly injected into-a. solution of 1.25 ml (0.01 rfio1e) of diethylaminosulfur' trifluoride in 51111 of methyle' r'iechlori'de cooled to 7 8. The reactionmixture'was then warmed to room temperature and mixed with cold w'atei. The lower layer was separated, washed with water, dried Mgsoo;

and distilled to give 0.93 g (78.% yield) of ethyl 2- fluoropropionateas 'a colorless liquid: bp 505'1 (50 mm); Fnmr (CC13F) s+1s4l pm (d, q, IF, J 49, 24,142). I

Anal. Calcdfor 0 1150,; c, 50.00; 11, 7.57; F, 15.83.

' Found: c, 50.11;11, 7.77; F, 16.01.

EXAMPLE 3 2-Fluoro-2-methylbutane A solution of 11.3 g (0.128 mole) of tert-pentanol in 25 ml of diethyleneglycol dimethyl ether was added dropwise to a solution of 16.1 g (0.1 mole) of diethylaminosulfur trifluoride in 100 ml of diethyleneglycol dimethyl ether cooled to 70. The most volatile portion of the reaction mixture was distilled out at reduced pressure (1 mm) into a receiver cooled with solid carbon dioxide. The condensate was redistilled to give 7.9 g (88%) of 2-fluoro-2-methylbutane (tertpentyl fluoride): bp 4546; F nmr (CCl F) 8 --1 39.2 pp (m)- Anal. Calcd for C H F: C, 66.62; H, 12.30; F, 21.08. Found: C, 66.81; H, 12.47; F, 21.72.

EXAMPLE 4 1,1-Difluoro-3-methylbutane A 1.72-g (0.02 mole) sample of isovaleraldehyde was slowly injected into a stirred solution of 2.5 ml (0.02 mole) of diethylaminosulfur trifluoride in ml of CCl F at 25. The reaction mixture was stirred for 30 min., and then mixed with 25 ml of water. The lower organic layer was separated, washedwith water, dried (MgSO and distilled to give 1.73 g (80%) of 1,1-difluoro-3-methylbutane as a colorless liquid: bp 59-60; F nmr (CCI F) 6 -115.5 ppm (d, t, 2F, J 58, 17 Hz).

Anal. Calcd for C H F C, 55.54; H, 9.33; F, 35.14. Found: C, 55.77; H, 9.61; F, 35.15.

EXAMPLE 5 2-Fluoro-3-butene and 1-Fluoro-2-butene A solution of 1.44 g (0.02 mole) of 3-butene-2-ol in 2 ml diethyleneglycol dimethyl ether was slowly injected into a stirred solution of 2.5 ml (0.02 mole) of diethylaminosulfur trifluoride in 10 ml of diethyleneglycol dimethyl ether cooled to 78. The reaction mix ture was warmed to 0 and the volatile products were distilled out into a cold trap at reduced pressure to give 1.3 ml of colorless liquid. Gas chromatographic analysis showed the product was a mixture containing 78% 2-t'luoro-3-butene and 22% of the isomeric 1-fluoro-2- butene. The product was redistilled to give 1.07 g of colorless liquid: bp 24-27; F nmrCCI F) 8 -l71.6 ppm (78%, d, q, d, d, J 46.7, 24, 13.0, 2.7 Hz) and 6 210.0 ppm (22%, t, m, J 50 Hz).

Anal. Calcd for C H F: C, 64.83; H, 9.53; F, 25.64. Found: C, 65.11; H, 9.79; F, 25.37.

This reaction was repeated, except that 2,2,4- trimethylpentane was used as solvent instead of dimethyl ether of diethyleneglycol to give 1.4 ml of a mixture containing 91% 2-fluoro-3-butene and 9% 1- fluoro-2-butene.

EXAMPLE 6 l-Fluoro-2-butene and 2-Fluoro-3-butene The procedure described for Example 5 was repeated, except that 2-butene-l-ol was used in place of 3-butene-2-ol. When diethyleneglycol dimethyl ether was used as solvent, 1.37 ml of a product containing 72% 2-fluoro-3-butene and 28% 1-fluoro-2-butene was obtained. When 2,2,4-trimethylpentane was used as solvent, 1.5 ml ofa product containing 64% 2-fluoro-3- butene and 36% 1-fluoro-2-butene was obtained.

EXAMPLE 7 2-Fluoro-2methyl-3-butyne A solution of 1.68 g (0.02 mole) of 2-methyl- 3 butyn-Z-ol in 2 ml of diethyleneglycol dimethyl ether was added slowly (5 min.) to a stirred solution of 2.5 ml (0.02 mole) of diethylaminosulfur trifluoride in 10 ml of diethyleneglycol dimethyl ether cooled to 78. The volatile portion of the reaction mixture was distilled out of the reaction mixture under reduced pressure (2 mm) and condensed in a cold trap. Redistillation gave 1.47 g of 2-fluoro-2-methyl-3butyne as a colorless liquid: bp 43 44"; F nmr cc1,F) s 129.3 ppm (septet, d, 1F, J 20, 5 Hz); H nmr (CCI F) 5 1.57 ppm (d, 6H, J 19.5 Hz) and 5 2.58 ppm (d, 1H, J 5 Hz).

Anal. Calcd for C H F: C, 73.44; H, 7.20; F, 19.36.

A solution of 3.08 g (0.02 mole) of exo-1,7,7- trimethylbicyclo[2.2.1lheptanol (borneol) in 15 ml of CCl F was slowly added to a solution of 2.5 ml (0.02 mole) of diethylaminosulfur trifluoride in 10 ml of CCl F cooled to 78. The reaction mixture was warmed to room temperature and water was added. The lower layer was separated, washed with water, 5% aqueous NaHCO- and water again, and then dried (MgSO Evaporation to dryness gave 2.87 g of a white solid composed of 20% camphene and 80% 3- fluoro-2,2,3-trimethylbicyclo[2.2.1lheptane. Recrystallization from 'pentane removed most of the -camphene to give 1.97 g of the fluoroheptane as colorless crystals: mp 93'94; F nmr (CCI F) 6 134.4 ppm (q, 1F, J 24 Hz); H nmr (CCl F), absorption due to methyl groups at 8 0.93 ppm (s) and 1.24 ppm (d, J 24 Hz).

Anal. Calcd for C H F: C, 76.87; H, 10.87; F,

12.16. Found: C, 76.99; H, 11.21; F, 11.97.

The reaction was repeated, using endo 1,7,7- trimethylbicyclo[2.2.l ]heptanol instead of the exo isomer to give 1.72 g of the same fluoroheptane, mp 93-94.

EXAMPLE 9 1Fluoro-2 isopropyl-5methylcyclohexane A solution of 3.12 g (0.02 mole) of (-)-menthol in 10 EXAMPLE 10 F luorocyclooctane A solution of 2.56 g (0.02 mole) of cyclooctanol in 2 ml CClgF was slowly added to a stirred solution of 2.5 ml (0.02 mole) of diethylaminosulfur trifluoride in 10 ml of CCI F at 78. The reaction mixture was warmed to room temperature and water was added. The lower and nuclear magnetic resonance indicated that the product consisted of 70% fluo rocycl ooctane and 30% cyclooctene. F nmr (CCl F) 8 160.5 ppm (d, p, 1F, J 46,

Hz). I V

H nmr for fluorocyclooctane) (CCl F) 6 4.55 ppm (d, 1H, 461-12) and& 1.2 to 2.4 (m, 141-1).

EXA'MPLE l1 Benzyl Fluoride A solution of 2.16 g (0.02 mole) of benzyl alcohol in ml CCl F was slowly injected into a solution of 2.5 ml

(0.02 mole) of diethylaminosulfur trifluoride in ml of CCl F cooled to 78. The reaction mixture was' warmed to room temperature and then slowly mixed with water. The lower layer was separated, washed with water, dried (MgSO and then distilled to give 1.65 g (75%) of benzyl fluoride, bp 139; F nmr (CCI F) 8 207.5 ppm (r, J 49 Hz). f

EXAMPLE l2 Benzyl Fluoride A solution of 0.90 ml (0.01 mole) of dimethylaminosulfur trifluoride in 5 ml methylene chloride was cooled to 78, and a solution 01 1.08 g (0.01

mole) of benzyl alcohol in 2 ml methylene chloride was slowly injected. The reaction mixture was warmed to room temperature and mixed with water. The lower layer was separated, dried (MgSO and analyzed by gas chromatography. and F nmr. The analyses showed that benzyl fluoride was formed in near-quantitative yield. I

EXAMPLE 13 4,4-Difluorohexane A solution of 16.1 g (0.1 mole) diethylaminosulfur" trifluoride in 10 ml CCl F was added dropwise to a solution of 11.4 g (0.1 mole) of 4-heptanone in 52 ml CCI F. Water, 5 11.1, was added as a catalyst, and the reaction mixture was stirred at room-temperature for'l week. Distillation gave 9.2 g (68%) of 4,4- difluorohexane, bp 90110, contaminated with a small amount of an immiscible liquid. The distillate was washed with water, dried (MgSO and redistilled to give 7.1 g of pure product: bp 11011l; n 1.3644; F nmr (CCI F) 98.6 ppm (p, 2F, J 15 Hz)/ H nmr (CCl F) 60.95 ppm (m, 6H), 1.55 ppm (m, 8l-1).

Anal. Calcd for C H F C, 61.74; H, 10.36; F, 27.90. Found: C, 62.13; H, 10.16; F, 28.07.

, EXAMPLE 14 1,1-Difluoroethylbenzene A solution of 2.5 ml (0.02 mole) of diethylaminosulfur trifluoride and 2.4 g (0.02 mole) of acetophenone in 12 ml of ethyleneglycol dimethyl ether was heated to reflux for hrs. and then cooled and mixed with water. The reaction mixture was extracted with CCl F, and the extract was dried (MgSO and distilled to give 0.8 g of recovered acetophenone, bp 108l12 (40 mm), and 1.2 g (66% yield, 42% conversion) of 1,1-difluoroethylbenzene: bp 64-65 (40 mm); F nmr (CCl F) 8 87.7 ppm (q, J 18 Hz).

Anal. Calcd for (3 1-1 1 C, 67.70; H, 5.67; F, 26.73. Found: C, 67.72; H, 5.73; F, 26.83.

EXAMPLE 15 3,3,7,7-Tetrafluoro-l,5-dimethylbicyclo[3.3.0]octane and 3,3 -Difluoro-l,5-dimethylbicyclo[3.3.0]octan- 7-one A solution of 8.3 g (0.05 mole) of 1,5-

dimethylbicyclo[3.3.0]octane-3,7-dione and 17.7 g (0.1 1 inch) of diethylaminosulfur trifluoride in 50 ml of benzene" was heated at reflux for 24 hr and then cooled and poured into 100 ml of water. The organic layer was separated, dried (MgSO and the benzene was distilled off. The residue was sublimed at 150 (1 mm) to give 6.3 g of a 80:20 mixture of 3,3,7,7- tetrafluoro-l,5-dimethylbicyclo[3.3.0]octane and 3,3- difluoro-l,5-dimethylbicyclo[3.3.0]octan-7-one.

The mixture was separated by liquid chromatography on an A1 0 column using pentane and ether. The tetrafluoride (3.7 g) was obtained as white, waxy crystals with a camphor-like odor: mp 106109; F nmr (CCl F) 8' 86.2 ppm (J 14 Hz) and 86.6 ppm (J pv Anal. Calcd for C 1-I F ':C, 57.14; H, 6.71; F, 36.15. Found: c,'57.12; H, 6.82; F, 36.14.

The difluoride (0.8 g) was obtained as light yellow crystals: mp 145l50; F nmr (CCl F) 8 80.9 and 81.0 ppm (J ='14 Hz); ir (KBr) 5.72 p. (C=0).

Anal. Calcd for C H F O: C, 63.81; H, 7.50; F, 20.19. Found: C, 63.07; H, 7.31; F, 20.87.

' EXAMPLE 16 v I Benzal Fluoride A 25-ml (0.2 mole) sample of diethylaminosulfur trifluoride was added dropwise over a period of 30 min.

. to a stirred solution of 21.2 g (0.2 mole) of benzaldehyde in ml of methylene chloride at 25. The reaction mixture was cooled to keep the temperature below 35. Stirring was continued for 2 hr, and then 100 ml of water was added. The lower layer was separated, washed with 5% NaHCO solution and then water, and dried (K CO Distillation gave 19.2 g (75%) ofbenzal fluoride; bp 57 (35 mm); "P nmr (CCl F) 8 110.9 ppm (d, J 57.5 Hz).

EXAMPLE 17 Benzoyl Fluoride EXAMPLE l8 Benzotrifluoride Diethylaminosulfur trifluoride, 8.05 g (0.05 mole) was added dropwise to'a solution of 2.44 g (0.02 mole) of benzoic acid in 20 ml of diethyleneglycol dimethyl ether cooled to 0. Sodium fluoride (1 g) was then added toremove the HF, and the reaction mixture was warmed to for 20 hr. The most volatile products were distilled from the reaction mixture and then redistilled to give 1.46 g (50%) of benzotrifluoride; .bp

102-.-l03; F nmr (CClgF).

EXAMPLE 19 Preparation of Benzhydryl 3-Fluoromethyl-7-(2- thienylacetamido)-3-cephem-4-carboxylate-l-oxide CH C1 To a solution of 0.483 g (3.0 mmoles) of diethylaminosulfur trifluoride in 10 mlof CH Cl at 78 under N was added a solution of 1.61 g (3.0 mmoles) of benzhydryl 3-hydroxymethyl-7-(2- thienylacetamido)-3-cephem-4-carboxylate-l-oxide in 50 ml of CH CI and the mixture was stirred at -78 for 0.5 hr, then poured into 100 ml of water. The CH Cl layer was dried (MgSO and evaporated in vacuo. The residue was chromatographed on silica gel with 9:1 CH c -acetone to yield 0.095 g of benzhydryl 3- fluoromethyl-7-(2-thienylacetamido)-3cephem-4-carboxylate-l-oxide in fractions 12-15, rf== 0.60 on tlc with 9:1 CH Cl -acetne; mp 205.5207.5 d; ir (CHCl 3450 (amide N-H), 1805 (B-lactam C=O), 1725 (ester C=O), 1680 (amide C=O), 1495 (amide 11 band), and 700 (aromatic) cm.

Anal. Calcd for C H N O S F: C, 60.22; H, 4.28; N, 5.20; F, 3.54. Found: C, 59.40; H, 4.29; N, 5.20; F, 3.60.

EXAMPLE Preparation of Benzhydryl 3-Difluoromethyl-7-(2- thienylacetamido)-3-cephem-4-carboxylate A solution of 0.518 g of benzhydryl 3-formyl-7-(2- thienylacetamido)-3-cephem-4-carboxylate and 1.0 ml of diethylaminosulfur trifluoride in 25 ml CH,C1 was stirred at 27 for 2.0 hr and then poured into 25 ml of water. The CH Cl phase was dried (MgSO and stripped in vacuo. The residue was chromatographed on silica with CHCl to yield 0.264 g (49%) of a 1:1 mixture of A'"':A benzhydryl 3-difluoromethyl-7-(2- thienylacetamido)-cephem-4-carboxylates; ir (CHCl 3450 (amide N-H), 1820 (B-lactam C=O), 1750 (ester C=O), 1695 (amide C=0), and 1510 (amide I1 band) cm; F nnir (CHCl;,) 8 116.43 (d (J 57 Hz), -CH E (one of A'+A isomers)) and and 115.82 (d (J 57 Hz), CH E (other isomer)); H nmr (CDCl 8 3.5 (2, m, C -C ll (A -isomefl), 3.74 (2, s, thienyl -'Cfl 4.94 (l, d (J 6 Hz), C fl), 5.91 (1, dd (J 6 Hz, .1 =10 Hz), C fi), 6.72 (1, t (J 57 Y (c )N--SF in I U J 111 U OH I cm? Hz), CflF and 7.3 (13, m, aryl thiophene H); uv max (C H OH) 265 nm (7400).

Anal. Calcd for C21H22N204S2F2: C, H, N, 5.18. Found: C, 59.82; H, 3.94; N, 5.01.

EXAMPLE 21 1,4-Diisopropyl-2-benzoyl Fluoride To 4.12 g (0.02 mole) 1,4-diisopropyl-2-benzoic acid in 25 ml cold benzene was added dropwise through a syringe 2.5 ml (0.02 mole) diethylaminosulfur trifluoride. The exothermic reaction was controlled by an ice bath. The solution was poured into water and extracted with benzene. The benzene was evaporated off yielding 3.94 g (96% yield) of the acid fluoride.

Anal: ir consistent with an authentic sample.

EXAMPLE 22 1 ,Z-Difluoroethane A solution of 620 mg (0.01 mole) of ethylene glycol in 2 ml of diethyleneglycol dimethyl ether was slowly added to a stirred solution of 2.5 ml (0.02 mole) of diethylaminosulfur trifluoride in 10 ml of diethyleneglycol EXAMPLE 23 l-Chloro-2-fluoroethane A solution of 1.61 g 0.02 mole) of ethylene chlorohydrin in 2 m1 diethyleneglycol dimethyl ether was slowly added to a solution of.2 .5 ml (0.02 mole) diethylaminosulfur trifluoride in 10ml of diethyleneglycol 3 dimethyl ether cooled to -7 8., The rea'ctionmixture 1 was warmed to room temperature, and the most volatile portionwasdistilledoutunder reduced pressure into a, 5

EXAMPLE :24

Diethylaminosulfur trifluoride, 2.5 ml (0.02 mole), was slowly injected into a stirred solution of 211 g of polyvinylbutyral (containing 21 weight of polymerized polyvinylalcohol in random distribution) in 100 ml ofethyleneglycol dimethyl ether cooled to 0. The reaction-mixture was slowly warmed to room temperature, and the solution was evaporated to dryness under reduced pressure, first at room temperature and then at 605. There was'obtained 2.1 g of rubbery film which 10 had improved oil and water repellent properties over -(D fl 0 y p the untreated polyvinylbutyral." Diethylaminosulfur trifluoride, 25 ml (ca.-O.2'mole M811" Foundi 3 was added dropwise to a stirred solution of 31.24 g (0.20 mole) of l-naphthaldehyde in 100 ml methylene .15 EXAMPLE 26 chloride at 25. The reaction mixture was stirred for 18 hr, and then mixed w.ithf100 "ml'of ice-water. The lower organic layer was'separated, washed with 5% NaHCO solution and then water, and dried (MgSO Distillation gave 16.4 g (72% yield, 46% conversion) of l- (difluoromethyl)naphthalene, bp 7879 (0.4 mm) and'1l.2 g"(3 6%) of recovered naphthaldehyde. f F hmr (CCL F) 5-1111 ppm (11,1 56 Hz H nmr (CClF) 8 8.3 to '7. l ppm (in, 7'aromatic'1-l) and 86.98 ppm(t,J=56Hz).

25 Anal. Calcd for C I-1 1 c, 74.15; H, 4.53; F, 21.32.

Found: c, 74.22; H, 4.16; 1 21.18.

I EXAMPILl I ZS L Y Fluorination ofPolyvinylbutyral/Polyvinyl Alcohol- I Fluol'inationv of Cellulose A throughly dried Soxhlet thimble, 33 mm in diameter and 94 mm long (3.90 g made of highly purified cellulose, was suspended in a solution of 2.5 ml diethylaminosulfur trifluoride in 250 m] methylene chloride at 25for 24 hr. The thimble was removed, washed with methylene chloride, and dried in vacuum. The" t 30 complished by using this process'are illustrated below.

H I o o cu n) 3)2 Hydroxyl or Dial kylaminosulfur Carbonyl Cpd. Trifluoride Product HOCH CH O-CH CH CN. l N--SF; .FCH CH- OCH CH,CN

l (CH; NCOCH CH OH N-SF; (CH hNCOcH CH F BrCH CH OH (nvC H l NSF BrCH CH F uocmcu Obi-SP FCH CH 1 equivalent CH OCHJIOH (CgH5)gNSF3 CHabCHgCF 1 equivalent ll I CH OCH,COH (CH3)2NSF3 CHQOCHCFQ 2 equivalents I @@ICH,COCH,CH,OH (cu-toms H=COC t -lTCOCH OH (CHzOzNSF; I N-COCH,F

ct-la cHa -Continued Hydroxyl or Dialkylaminosulfur Carbonyl Cpd. Trifluoride Product H(CH,).0H s): H)|F 2 equivalents HO(CH,) OH (CH3):NSF3 F(CH;)4OH

l equivalent HOCH-ECH OH (CH3):NSF3 FCH,CCH,F 2 equivalents (HOCH,CH,),S (CH3):NSF;| (FCH=CH;),S

2 equivalents HOCH Cl'hNO, (CH )=NSF; FCH,CH,NO,

d- 91N 51 HO F HO F I claim: taken together are -(CH,) or (CH with a l. A process for producing a fluorinated compound comprising contacting a compound of the formula wherein each of R and R, alike or different, is a primary alkyl group of up to 4 carbon atoms or when is a monohydric alcohol.

ll ll k UNITED STATES PATENT OFFICE CETEFECATE OF CORRECTION PATENT NO. 5,914,265 DATED 1 October 21, 197

|NVENTOR(5) I William Joseph Middleton it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

C010, 1, line 21 "5059" should be "3058;

Col. 5, line 47 "'cc1 F)" should be "(001 1 Col. 7', line 4-5 "52" should be --25---;

C01. 7, line 51 "Hz)/" should be --Hz);--;

001. 8, line 1 "67.70" should be "67.60";

col; 9, line 50 "cn c should be --CH Cl Col, 10, line 2 "CH F should be -CHE Col. 10, line 3 "CHE- should be -CH Col, 11, line 22 "hmr (CZCL F) should be --nmr (CCl F)-;

Col. 12, second formula from bottom should CH COCH CH 0 1| be -CH COCH2CH2F;

Col' l t, line 40 "-35C." should be --+35C.--.

I I Signed and Scaled this twenty-fifth Day of May 1976 [SEAL] A ttes t:

RUTH C. MASON C. MARSHALL DANN Atresting Officer Commissioner uflalvnts and Trademarks t 

1. A PROCESS FOR PRODUCING A FLUORINATED COMPOUND COMPRISING CONTACTING A COMPOUND OF THE FORMULA
 2. The process of claim 1 carried out at -80* to -35*C.
 3. The process of claim 1 wherein the said reactant is a polyhydric alcohol.
 4. The process of claim 1 wherein the said reactant is a monohydric alcohol. 